Topology‐Templated Synthesis of Crystalline Porous Covalent Organic Frameworks

Here we report a strategy for the synthesis of crystalline porous c ovalent organic frameworks via t opology-templated polymerization. The template is based on imine-linked frameworks and their (001) facet s seed the C=C bond formation reaction to constitute 2D sp 2 carbon-conjugated frameworks. This strategy is applicable to templates with different topologies, enables designed synthesis of frameworks that cannot be prepared via direct polymerization, and creates a series of sp 2 carbon frameworks with tetragonal, hexagonal, and kagome topologies. The sp 2 carbon frameworks are highly luminescent even in the solid state and exhibit topology dependent pi transmission and exciton migration ; these key fundamental pi functions are unique to sp 2 carbon-conjugated frameworks and c annot be accessible by imine-linked frameworks, amorphous analogues, and 1D conjugated polymers. These results demonstrate an unprecedented strategy for structural and functional designs of covalent organic frameworks.